KR20120034508A - Segment-in-series type sofc sub-module, preparation method thereof and segment-in-series type sofc module using the same - Google Patents

Abstract

PURPOSE: A segment type solid oxide fuel cell sub-module is provided to be able to have high power, and to improve starting spend and thermal cycle resistance. CONSTITUTION: A segment type solid oxide fuel cell sub-module comprises a porous tubular supporter(11), an anode(12) formed on outside of the porous tubular supporter, an electrolyte layer(13), a cathode(14), and an interconnect(15). The porous tubular supporter is manufactured through extrusion, drying, heat-treating, and sintering processes. The paste is manufactured through mulling the mixture of uniformized and powderized calcia-stabilized zirconia, and activated carbon powder, binder, and distilled water. The segment type solid oxide fuel cell comprises the plurality of segmented type solid oxide fuel cell sub-modules.

Description

Segmented Solid Oxide Fuel Cell Submodule, Manufacturing Method Thereof and Segmented Solid Oxide Fuel Cell Module Using The Same

The present invention relates to a segmented solid oxide fuel cell submodule, a method for manufacturing the same, and a segmented solid oxide fuel cell module using the same. More specifically, the present invention relates to a segmented solid oxide fuel cell submodule, and more particularly, exhibits high gas permeability and excellent compressive strength. Segmented solid oxide fuel cell submodule using a tubular support, a method of manufacturing the same and a segmented solid oxide fuel cell module using the same.

Solid Oxide Fuel Cell (SOFC) produces electricity by electrochemical reaction between fuel (H ₂ , CO) and air (oxygen) at high temperature of 600 ~ 1000 ℃ using solid ceramic as electrolyte. As a fuel cell, there is an advantage in generating power generation efficiency and excellent economic efficiency among the existing power generation technology.

Since SOFC and electrolyte are in solid state, it can be manufactured in various types of cells such as flat plate and cylinder, and classified into anode support type, cathode support type, and electrolyte support type according to fuel cell support. do.

Flat SOFCs have high power density, high productivity, and thin electrolyte, but require gas sealing using a separate sealant, and due to the use of metal connecting materials at high temperatures, electrode efficiency is reduced due to chromium volatilization. However, it has a disadvantage of lacking reliability due to low resistance to thermal cycles. Moreover, since flat panel SOFCs are not only difficult to manufacture large-area cells but also easy to manufacture large-capacity stacks, solving these problems becomes a key to practical use.

Cylindrical SOFCs are evaluated as SOFC designs closest to commercialization because they do not require gas sealing, have excellent mechanical strength, and have been tested for reliability in various test items. However, the cylindrical SOFC has a disadvantage of high internal resistance and low power density because of a long current path. In addition, since the voltage output from the module, which is a collection of cells, is low, the power conversion loss during operation is large, and as a result, there is a weakness in efficiency.

Currently, SOFC systems for power generation above 20 kW are mostly adopting stacks using cylindrical or improved cylindrical cells, and in the case of 20 kW or lower, flat cells are also adopted.

On the other hand, the segment-in-series type SOFC is one of the most advantageous and economical types of the improved cell type to compensate for the shortcomings of the conventional SOFC cell type for power generation. The cell is composed of nodes made of several cells. Since the segmented SOFC cell is a module in which unit cells are connected in series, high-voltage, low-current output enables high-efficiency generation, and can reduce the stack volume, thereby simplifying the system. In addition, segmented SOFC cells can reduce stack manufacturing costs, apply low-cost wet coating processes that can be mass-produced, and minimize gas sealing problems by only gas sealing the edges of cylindrical cells. There is an advantage that the large area is easy through the increase in the length of the cylindrical cell support.

It is an object of the present invention to provide a segmented solid oxide fuel cell submodule using a porous tubular support having high gas permeability and excellent compressive strength, a method of manufacturing the same, and a segmented solid oxide fuel cell module using the same.

Another object of the present invention is to provide a segmented solid oxide fuel cell submodule capable of high output, increased start-up speed and heat cycle resistance, a manufacturing method thereof, and a segmented solid oxide fuel cell module using the same.

In order to achieve the above object, the present invention is a segmented solid oxide fuel cell submodule comprising a porous tubular support, a fuel electrode, an electrolyte layer, an air electrode, and a connecting material formed on the porous tubular support, the porous tubular support is uniform and powdered A segment-type solid oxide fuel cell submodule is prepared by extruding, drying, heat treating, and sintering a paste prepared by kneading a mixture of calcified stabilized zirconia (CSZ) and activated carbon powder, a binder, and distilled water. to provide.

The present invention also provides a porous tubular support using a paste comprising a mixture of homogenized and powdered calcia stabilized zirconia (CSZ) and activated carbon powder, a binder and distilled water (S1); Forming a fuel electrode on the porous tubular support (S2); Forming an electrolyte layer on the anode (S3); And forming a cathode on the electrolyte layer (S4) and forming a connection material for electrical connection (S5).

The present invention also provides a segmented solid oxide fuel cell module including a plurality of segmented solid oxide fuel cell submodules of the present invention.

The present invention uses a porous tubular support that exhibits high gas permeability and excellent compressive strength, thereby enabling high output, increased start-up speed and heat cycle resistance, and a segmented solid oxide fuel cell submodule, a method of manufacturing the same, and a segmented solid using the same. Provided is an oxide fuel cell module.

1 is a cross-sectional view of a segmented solid oxide fuel cell submodule manufactured according to one embodiment of the present invention.
Figure 2 is a photograph showing a process of extruding a porous tubular support in Example 1 of the present invention.
Figure 3 is after forming the anode and the electrolyte layer on the porous tubular support in Example 1 of the present invention (a) anode coating surface, (b) electrolyte layer coating surface, (c) anode coating cross section and (d) anode Scanning electron micrographs taken of the electrolyte layer coating cross section.
4 is a scanning electron micrograph taken on the surface and the cross-section of the air electrode composed of a multilayer of LSM-YSZ / LSM / LSCF formed on the porous tubular support in Example 1 of the present invention.
5 is a photograph of a wired segmented solid oxide fuel cell submodule manufactured in Test Example 1 of the present invention.
6 is a graph showing the results of measuring the open circuit voltage and the cell performance of the segment type solid oxide fuel cell unit cell and the segment type solid oxide fuel cell submodule in Test Example 1 of the present invention.

Hereinafter, a segmented solid oxide fuel cell submodule of the present invention, a manufacturing method thereof, and a segmented solid oxide fuel cell module using the same will be described in detail with reference to the accompanying drawings.

1 is a cross-sectional view of a segmented solid oxide fuel cell submodule manufactured according to one embodiment of the present invention.

The present invention includes a segmented solid oxide fuel cell submodule 100 including a porous tubular support 11, a fuel electrode 12 formed on an upper portion of the porous tubular support, an electrolyte layer 13, an air electrode 14, and a connecting member 15. )as,

As the porous tubular support 11, a paste prepared by kneading a mixture of homogenized and powdered calcia stabilized zirconia (CSZ) and activated carbon powder, a binder, and distilled water is used through extrusion, drying, heat treatment, and sintering. do.

In the segmented solid oxide fuel cell submodule 100, the porous tubular support 11 serves as a flow path of fuel / reactant while forming a frame of a cell, and is composed of a material having no electrical conductivity because it connects two or more unit cells. do.

The porous tubular support 11 used in the present invention is manufactured using a paste containing a mixture of homogenized and powdered calcia stabilized zirconia (CSZ) and activated carbon powder, thereby exhibiting high porosity and excellent compressive strength.

As shown in FIG. 1, the segmented solid oxide fuel cell submodule 100 according to the present invention includes a fuel electrode 12, an electrolyte layer 13, an air electrode 14, and a connecting member 15 on the porous tubular support 11. ) Are sequentially formed and manufactured.

The anode 12 is manufactured using a slurry prepared by mixing nickel oxide (NiO) powder, yttria stabilized zirconia (YSZ) powder, a binder, a homogeneous agent, a dispersant, a plasticizer and a solvent.

The electrolyte layer 13 is formed by coating a slurry prepared by mixing yttria stabilized zirconia (YSZ) powder, a binder, a homogeneous agent, a dispersant, a plasticizer and a solvent on the anode.

The cathode 14 is formed of a multilayer structure cathode in which an LSM-YSZ layer, an LSM layer, and an LSCF layer are sequentially formed.

As shown in FIG. 1, the segmented solid oxide fuel cell submodule 100 includes a plurality of unit cells including a fuel electrode 12, an electrolyte layer 13, and an air electrode 14 formed on a porous tubular support 11. It is electrically connected by the connecting material 15.

The connecting member 15 is formed in the segmented solid oxide fuel cell submodule 100 to electrically connect the anode of the unit cell and the cathode of another unit cell.

In one embodiment of the present invention, the connecting member 15 may be formed using a silver-glass paste, but may be used without limitation, materials commonly used in the art to which the present invention pertains.

Hereinafter, a method of manufacturing the segmented solid oxide fuel cell submodule 100 of the present invention will be described.

First, a porous tubular support 11 is prepared using a paste comprising a mixture of homogenized and powdered calcia stabilized zirconia (CSZ) and activated carbon powder, a binder and distilled water (S1).

Calcia stabilized zirconia (CaO-stabilized ZrO ₂ : CSZ) powder is used as a main raw material for preparing the porous tubular support 11, and activated carbon powder is used as a pore former, and 100 wt% of CSZ is used. 10-15 weight% of activated carbon powder is mixed. When the activated carbon powder is used in less than 10% by weight, there is a problem that the porosity of the porous tubular support 11 is lowered, and when the activated carbon powder is used in excess of 15% by weight, the porosity is increased but the compressive strength is lowered.

A mixture of CSZ and activated charcoal powder mixed according to the above-mentioned content is prepared in a slurry state and homogenized by ball milling. At this time, ethanol is used as a solvent, and since ethanol is fast drying, the work can be performed quickly when dried in a dryer after ball milling. Ball milling is performed for two weeks using high purity zirconia balls, so that the mixture of CSZ and activated carbon powder can be as uniform as possible.

Subsequently, the mixture of homogenized CSZ and activated carbon powder is dried in a hot plate and then ground to powder.

Then, a paste is formed by kneading by adding a binder and a solvent to the powdered mixture. As the binder, YB-131D, which is a comprehensive binder, may be used, and YB-131D is widely known as an organic binder including methyl cellulose and hydroxypropyl methyl cellulose, a plasticizer and a lubricant. The binder serves to bind the powdered mixture and to form pores with the activated carbon. The binder adds 7 to 8% by weight based on 100% by weight of the mixture of CSZ and activated carbon, but when used in less than 7% by weight, the formability of the porous tubular support 11 is reduced and the pore formation rate is lowered. If it exceeds 8% by weight, many pores are formed, but the strength decreases and cracks occur during the sintering process. Distilled water may be used as the solvent, and 45.5-50 wt% of distilled water is added based on 100 wt% of the mixture of CSZ and activated carbon. When the distilled water content is less than 45.5% by weight, there is a portion remaining as a powder, not a paste, when kneading, and when the porous tubular support 11 is extruded in a subsequent process, the extrusion is difficult. In addition, when the use content of distilled water exceeds 50% by weight, the paste adheres to the screw surface of the extruder when the porous tubular support 11 is extruded, so that extrusion is difficult to be performed, and there is a fear of cracking during sintering.

Next, the paste formed according to the above-described process is extruded into the porous tubular support 11 using the extruder 20 shown in FIG. 2, so that the moisture of the paste is evenly distributed before extrusion, for example, refrigerated for 24 hours. It is desirable to go through the storage process.

The extruded porous tubular support 11 is, for example, formed in a tubular shape having an outer diameter of 22 mm and an inner diameter of 16 mm, but may cause warpage or cracking due to evaporation of the solvent during drying. Therefore, in order to prevent this, a metal bar (not shown), such as a steel bar, is inserted into the tube of the porous tubular support 11 and dried at room temperature while rolling in a rolling dryer.

Thereafter, the dried porous tubular support 11 is heat treated to perform a process of completely burning the binder and the activated carbon component added to the porous tubular support. That is, the binder is burned by heat treatment at 300 to 400 ° C. for 4 to 6 hours, and then the activated carbon is burned by heat treatment at 700 to 800 ° C. for 2 to 4 hours.

Finally, the porous tubular support 11 is heat-treated as described above to complete the porous tubular support 11 by sintering at 1350 ~ 1450 ℃. Since the heat treatment temperatures of the fuel electrode 12, the electrolyte 13, and the air electrode 14 coated on the surface of the porous tubular support 11 are 1000 ° C., 1400 ° C., and 1150 ° C., respectively, the heat treatment temperature of the electrolyte having the highest heat treatment temperature is 1400. It is preferable to perform sintering at 1350-1450 degreeC which is near to degreeC. At a lower temperature, the sintering is not performed well, so that the pores become large and the strength is lowered. When sintering at a higher temperature, the porosity is lowered, resulting in a problem of poor performance.

The porous tubular support 11 manufactured according to the above-described method exhibits high gas permeability and excellent compressive strength, so that when used in a segmented solid oxide fuel cell submodule and a module using the same, high output is possible, and a running speed and a thermal cycle A segment type solid oxide fuel cell submodule having increased resistance and a module using the same can be manufactured.

Next, the anode 12 is formed on the porous tubular support 11 (S2).

The anode 12 is a nickel oxide (NiO) / yttria stabilized zirconia (YSZ) mixed powder 18 ~ 23% by weight, binder 3 ~ 7% by weight, homogeneous 0.5 ~ 3% by weight, dispersant 0.05 ~ 0.3% by weight, plasticizer 4 The slurry may be prepared by mixing? 7 wt% and 65? 70 wt% of the solvent, and then coating the porous tubular support 11 by using a dip coating method or the like. Since the anode 12 is preferably heat treated for about 1.5 to 4.5 hours at about 900 ~ 1100 ℃.

In one embodiment of the invention, the nickel oxide (NiO) / yttria stabilized zirconia (YSZ) mixed powder is prepared by mixing 66% by weight of nickel oxide (NiO) powder and 34% by weight of yttria stabilized zirconia (YSZ) powder. Can be.

In addition, the solvent may be a mixture of 36% by weight of toluene and 64% by weight of isopropyl alcohol.

Next, the electrolyte layer 13 is formed on the fuel electrode 12 (S3).

2 to 4 wt% of yttria stabilized zirconia (YSZ) powder, 0.2 to 0.4 wt% of binder, 0.04 to 0.08 wt% of homogeneous agent, and 0.005 to 0.009 wt% of dispersant to form electrolyte layer 13 on the anode 12 A slurry is prepared by mixing 0.2 to 0.4 wt% of a plasticizer and 94 to 98 wt% of a solvent, and the prepared slurry is coated on the anode 12 by using a vacuum slurry coating method. Since the electrolyte layer 13 is preferably heat treated for about 3 to 7 hours at about 1250 ~ 1450 ℃.

In one embodiment of the present invention, a mixture of 38% by weight of toluene and 62% by weight of isopropyl alcohol may be used as the solvent.

Next, the cathode 14 is formed on the electrolyte layer 13 (S4).

In the present invention, the cathode 14 may be a multilayer structure cathode in which an LSM-YSZ layer, an LSM layer, and an LSCF layer are sequentially formed on the electrolyte layer 13.

In order to coat the cathode having a multi-layered structure as the cathode 14, Ls ₂ O ₃ , SrCO ₃ , Co (NO ₃ ) ₂ 6H ₂ O, Fe ₂ O ₃ , and MnO ₂ raw powders were quantitatively determined for solid phase reaction ( Solid State Reaction Method (La, Sr) MnO ₃ Powder, (La, Sr) (Co, Fe) O ₃ powder is prepared.

(La, Sr) MnO ₃ 18-23 wt% of Yttria stabilized zirconia (YSZ) mixed powder, 3-7 wt% of binder, 0.5-3 wt% of homogenizer, 0.05-0.3 wt% of dispersant, 4-7 wt% of plasticizer and 65-70 wt% of solvent To prepare a slurry to form the LSM-YSZ layer by mixing.

(La, Sr) MnO ₃ / Yttria stabilized zirconia (YSZ) powder mixture is (La, Sr) MnO ₃ One prepared by mixing 50% by weight of powder and 50% by weight of yttria stabilized zirconia (YSZ) may be used.

In the same manner, (La, Sr) MnO ₃ powder 18-23 wt%, binder 3-7 wt%, homogenizer 0.5-3 wt%, dispersant 0.05-0.3 wt%, plasticizer 4-7 wt% and solvent 65-70 wt% Mix% to make a slurry to form an LSM layer.

Similarly (La, Sr) (Co, Fe) O ₃ powder 18-23% by weight, binder 3-7%, homogenizer 0.05-3%, dispersant 0.05-0.3%, plasticizer 4-7% and solvent 65 70 wt% of the mixture is prepared to form a slurry to form an LSCF layer.

In one embodiment of the present invention, a mixture of 36% by weight of toluene and 64% by weight of isopropyl alcohol may be used as the solvent used in the slurry for forming the air electrode.

After masking the remaining portions except for the portion where the cathode 14 of the porous tubular support 11 is to be formed, a slurry for forming the LSM-YSZ layer, a slurry for forming the LSM layer, and a slurry for forming the LSCF layer It is possible to form a multilayer structure cathode by immersion coating 2 times-1 time-2 times sequentially.

Finally, the connection member 15 is formed for electrical communication of the segmented solid oxide fuel cell submodule (S5).

Segmented solid oxide fuel cell submodule 100 according to the present invention is a unit cell consisting of a node including a connecting electrode 12, an electrolyte layer 13 and the air electrode 14 on the porous tubular support (11) It has a structure electrically connected in series by the connecting material 15. That is, the connector 15 electrically connects the anode of the unit cell and the cathode of the other unit cell in the segmented solid oxide fuel cell submodule 100 to enable electrical communication between the unit cells.

In one embodiment of the present invention, the connecting member 15 may be formed by coating a silver-glass paste.

The silver-glass paste may be prepared by mixing 53 to 57 wt% silver powder, 4 to 8 wt% glass powder, 3 to 6 wt% binder, and 31 to 35 wt% solvent.

The connecting member 15 should have excellent electrical conductivity and ensure gas sealing properties, and may exhibit excellent electrical conductivity by silver powder included in the silver-glass paste, and may exhibit gas sealing effect by glass powder. have.

In the present invention, the binder used in the preparation of the slurry for forming the anode 12, the electrolyte layer 13, and the cathode 14 may be BM1, BM2, PVB, etc., and the homogeneous agent may use Triton X-100. The dispersant may use SN-dispersant, the plasticizer may use dibutyl phthalate, and the solvent may use a mixed solvent of toluene and isopropyl alcohol.

Methyl cellulose may be used as the binder used in the production of the silver-glass paste for forming the connecting member 15, and α-terpinol may be used as the solvent.

Hereinafter, preferred embodiments of the present invention will be described in detail.

(1) porosity Tubular  Preparation of the Support

1000 g of calcia stabilized zirconia and 150 g of activated carbon powder were mixed. Ethanol was added and homogenized by high-purity zirconia balls for 2 weeks by ball milling, dried on a hot plate, and ground using a grinder. The paste was prepared by kneading 75 g of YB-131D and 500 g of distilled water as a binder to a mixture of calcia stabilized zirconia and activated carbon powder, and refrigerated the paste for 24 hours to distribute the moisture evenly. Extruded as shown. Then, a metal bar was inserted into the extruded porous tubular support hole and dried at room temperature in a rolling dryer. Thereafter, the binder and the activated carbon were heat-treated at 350 ° C. for 5 hours and heat treated at 750 ° C. for 3 hours, and then calcined at 1100 ° C. for 3 hours to prepare a porous tubular support.

(2) Segment  Solid oxide fuel cell unit cell single cell Manufacturing

NiO / YSZ mixed powder (fuel cell material) 20.5 wt%, PVB binder 5.1 wt%, Triton X-100 1.4 wt%, SN-dispersant 0.16 wt%, Dibutyl for coating the anode on the prepared porous tubular support A slurry having a solid content of 20% by weight was prepared by mixing 5.34% by weight of phthalate and 67.5% by weight of toluene and isopropyl alcohol mixed solvent, and coated the anode by using a dip coating method on the porous tubular support. Thereafter, to form an electrolyte layer on the anode, 3 wt% of yttria stabilized zirconia (YSZ) powder, 0.3 wt% of binder (BM1 and BM2 1: 1 weight ratio), Triton X-100 0.06 wt%, and SN-dispersant 0.007 wt% , 0.3% by weight of dibutyl phthalate and 96.33% by weight of toluene and isopropyl alcohol mixed solvent were prepared to prepare a slurry having a solid content of 3% by weight, and the slurry was coated on the anode using vacuum slurry coating method, and then 5 hours at 1350 ° C. Sintered. After forming the anode and the electrolyte layer on the porous tubular support as described above, a scanning electron microscope photograph was taken of the anode and the electrolyte coating surface, the anode coating cross section and the anode and the electrolyte layer coating cross section, and shown in FIG. 3. Thereafter, in order to coat the multilayer structure cathode of LSM / YSZ-LSM-LSCF, each slurry was prepared using LSM / YSZ, LSM, and LSCF powder (fuel cell material). After masking all parts except the part to be coated with the cathode by Teflon, the coating was immersed sequentially in two YSZ-LSM slurries, one LSM slurry, and two LSCF slurries. At this time, LSM and LSCF were coated by changing the top and bottom during the second coating to make the coating thickness constant. As described above, a slurry-type solid oxide fuel cell unit cell according to the present invention was manufactured by forming a cathode by heat treatment at 1150 ° C. for 3 hours after slurry coating. A scanning electron microscope photograph was taken of the surface (Fig. 4 (a)) and the cross section (Fig. 4 (b)) of the air electrode composed of a multilayer of LSM-YSZ / LSM / LSCF and are shown in Fig. 4. When the cathode having a thickness of about 30 μm constitutes an electrode having sufficient porosity to be injected, the composite layer of LSM / YSZ shows good interfacial formation with the electrolyte. It can be seen that it is made of a multilayer.

(3) Segment  Fabrication of Solid Oxide Fuel Cell Submodules

A silver-glass paste having a weight ratio of silver to glass of 9: 1 was prepared by mixing 55.4 wt% silver powder, 6.2 wt% glass powder, 4.6 wt% methyl cellulose, and 33.8 wt% α-terpinol. Then, after masking using a masking tape except for a portion of the segment-type solid oxide fuel cell in which the connection material is to be coated between the nodes of the unit cells, the silver-glass paste is coated three times. At this time, the coating is dried once so that the first coated portion is not peeled off. Thereafter, the commercial silver paste was coated once, dried at 80 ° C. for 30 minutes in a drying oven, and heat treated at 800 ° C. for 10 minutes to prepare a segmented solid oxide fuel cell submodule according to the present invention.

Test Example  One - Segment  Solid oxide fuel cell unit cell and Segment  Open Circuit Voltage and Cell Performance Measurement of Solid Oxide Fuel Cell Submodule

In a segmented solid oxide fuel cell sub-module manufactured by connecting segmented solid oxide fuel cell unit cells with a connecting material, a silver wire is wired to a positive electrode and a cathode partially coated with a connecting material and By connecting the platinum wire, the voltage drop was measured while varying the current density flowing through the module using a DC electrode and a power supply. The temperature of the furnace for measuring unit cell performance was raised to 2 ° C / min, and performance measurement was performed at 650, 700, 750, and 800 ° C. At this time, 3% humidified hydrogen as fuel was supplied with air as an oxidant. Segmented solid oxide fuel cell unit cells have open circuit voltages of 0.97, 1.00, 1.00, and 1.00 V at operating temperatures of 650, 700, 750, and 800 ° C, respectively, and battery performance of 53, 92, 137, and 197 mW, respectively. The performance per unit area is 31, 57, 82, 118 mW / cm ² . Segmented solid oxide fuel cell submodules have open circuit voltages of 1.33, 1.57, 1.82, and 1.90 V at operating temperatures of 650, 700, 750, and 800 ° C, respectively, and battery performance of 50, 103, 201, and 319 mW, respectively. Performance per unit area was 17, 35, 68, 109 mW / cm ² . 5 is taken of the wired segmented solid oxide fuel cell submodule, and the open circuit voltage and the cell performance of the segmented solid oxide fuel cell unit cell and the segmented solid oxide fuel cell submodule are measured. (a) and (b) of FIG. 6.

As described above, it can be seen that the segmented solid oxide fuel cell submodule of the present invention is capable of higher output than the segmented solid oxide fuel cell unit cell.

Although the present invention has been described with reference to preferred embodiments, the present invention is not limited to the above-described specific embodiments, and those skilled in the art to which the present invention pertains have various modifications without departing from the technical spirit. You can do it. Therefore, the scope of the present invention should be construed as defined by the appended claims rather than the specific embodiments.

Explanation of symbols on the main parts of the drawings
11 porous tubular support 12 fuel electrode
13 electrolyte layer 14 air cathode
15: connecting material
100: segment type solid oxide fuel cell submodule

Claims (15)

A segmented solid oxide fuel cell submodule comprising a porous tubular support, a fuel electrode, an electrolyte layer, an air electrode, and a connecting member formed on an outer surface of the porous tubular support,
The porous tubular support is a segment prepared by extruding, drying, heat treating and sintering a paste prepared by mixing a mixture of homogenized and powdered calcia stabilized zirconia (CSZ) and activated carbon powder, a binder and distilled water. Solid oxide fuel cell submodule.
The method according to claim 1,
The porous tubular support was homogenized and powdered by mixing 10-15% by weight of activated carbon powder with respect to 100% by weight of calcia stabilized zirconia (CSZ) powder, and then distilled water based on 100% by weight of the mixture of powdered CSZ and activated carbon powder. Segmented solid oxide fuel cell submodule, characterized in that prepared using a paste prepared by adding and mixing 45.5-50% by weight and 7-8% by weight binder.
The method according to claim 1,
The anode is a nickel oxide (NiO) / yttria stabilized zirconia (YSZ) mixed powder 18 ~ 23% by weight, binder 3 ~ 7% by weight, homogeneous 0.5 ~ 3% by weight, dispersant 0.05 ~ 0.3% by weight, plasticizer 4 ~ 7 weight Segmented solid oxide fuel cell submodule, characterized in that formed by coating a slurry prepared by mixing a mixture of 65% to 70% by weight on a porous tubular support.
The method according to claim 1,
The electrolyte layer is 2-4 wt% of yttria stabilized zirconia (YSZ) powder, 0.2-0.4 wt% binder, 0.04-0.08 wt% homogeneous agent, 0.005-0.009 wt% dispersant, 0.2-0.4 wt% plasticizer and 94-98 solvent Segmented solid oxide fuel cell submodule, characterized in that the coating on the anode using a slurry prepared by mixing the weight%.
The method according to claim 3 or 4,
The binder is used alone or mixed with BM1, BM2 or PVB, the homogeneous agent is Triton X-100, the dispersant is SN-dispersant, the plasticizer is dibutyl phthalate, the solvent is toluene Segmented solid oxide fuel cell submodule, characterized by using a mixed solvent of isopropyl alcohol.
The method according to claim 1,
The cathode is a segmented solid oxide fuel cell submodule, wherein the cathode is a multilayer structure cathode in which an LSM-YSZ layer, an LSM layer, and an LSCF layer are sequentially formed on an electrolyte layer.
The method of claim 6,
The LSM-YSZ layer is (La, Sr) MnO ₃ 18-23 wt% of Yttria stabilized zirconia (YSZ) mixed powder, 3-7 wt% of binder, 0.5-3 wt% of homogenizer, 0.05-0.3 wt% of dispersant, 4-7 wt% of plasticizer and 65-70 wt% of solvent Segmented solid oxide fuel cell submodule, characterized in that formed using a slurry prepared by mixing.
The method of claim 6,
The LSM layer comprises (La, Sr) MnO ₃ powder 18-23% by weight, binder 3-7%, homogenizer 0.5-3%, dispersant 0.05-0.3%, plasticizer 4-7% and solvent 65-70 Segmented solid oxide fuel cell submodule, characterized in that formed using a slurry prepared by mixing the wt%.
The method of claim 6,
The LSCF layer is (La, Sr) (Co, Fe) O ₃ powder 18-23% by weight, binder 3-7%, homogeneous agent 0.05-3%, dispersant 0.05-0.3%, plasticizer 4-7% by weight And a slurry prepared by mixing 65 to 70 wt% of the solvent.
10. A segmented solid oxide fuel cell module comprising a plurality of segmented solid oxide fuel cell submodules according to any one of claims 1 to 9.
Preparing a porous tubular support using a paste comprising a mixture of homogenized and powdered Calcia stabilized zirconia (CSZ) and activated carbon powder, a binder and distilled water (S1);
Forming a fuel electrode on the porous tubular support (S2);
Forming an electrolyte layer on the anode (S3);
Forming an air electrode on the electrolyte layer (S4); And
Forming a connecting material for the electrical connection (S5)
Segmented solid oxide fuel cell submodule manufacturing method comprising a.
The method of claim 11,
Preparing the porous tubular support (S1),
10 to 15% by weight of the activated carbon powder is mixed with respect to 100% by weight of the calcia stabilized zirconia (CSZ) powder to prepare a slurry and homogenized by ball milling;
Pulverizing and drying the mixture of the uniformed CSZ powder and activated carbon powder to powder;
Adding 45.5-50 wt% of distilled water and 7-8 wt% of binder to the powdered mixture based on 100 wt% of the powdered mixture and kneading to prepare a paste, followed by extrusion into a tubular support;
Inserting a metal bar into the tube of the extruded tubular support and drying at room temperature while rolling;
Heat-treating the dried tubular support to completely burn the binder and activated carbon component added to the tubular support; And
Sintering the heat-treated tubular support at 1350 ~ 1450 ℃ characterized in that it comprises a step of producing a segmented solid oxide fuel cell submodule.
The method of claim 12,
And uniformizing the mixture of the CSZ powder and the activated carbon powder in a slurry state by ball milling is performed by adding ethanol to the segment type solid oxide fuel cell submodule.
The method of claim 12,
A method of manufacturing a segmented solid oxide fuel cell submodule, wherein the paste is refrigerated so as to distribute moisture evenly before extruding into the tubular support.
The method of claim 12,
The heat treatment step of the tubular support is a method of manufacturing a segment-type solid oxide fuel cell submodule, characterized in that the process consisting of a heat treatment for 4-6 hours at 300 ~ 400 ℃, and a heat treatment for 2 to 4 hours at 700 ~ 800 ℃. .

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